EP2142478A2 - Procede de preparation d'une solution colloïdale de zircone - Google Patents
Procede de preparation d'une solution colloïdale de zirconeInfo
- Publication number
- EP2142478A2 EP2142478A2 EP08788129A EP08788129A EP2142478A2 EP 2142478 A2 EP2142478 A2 EP 2142478A2 EP 08788129 A EP08788129 A EP 08788129A EP 08788129 A EP08788129 A EP 08788129A EP 2142478 A2 EP2142478 A2 EP 2142478A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- zirconia
- suspension
- zirconia particles
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 44
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 10
- 239000011707 mineral Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 39
- 239000002244 precipitate Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 14
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical group CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 238000010348 incorporation Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 3
- 239000002609 medium Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 22
- 239000002105 nanoparticle Substances 0.000 description 16
- 238000005119 centrifugation Methods 0.000 description 15
- 229920000126 latex Polymers 0.000 description 13
- 239000002689 soil Substances 0.000 description 13
- 239000002966 varnish Substances 0.000 description 13
- -1 alkyl methacrylates Chemical class 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- JHQVCQDWGSXTFE-UHFFFAOYSA-N 2-(2-prop-2-enoxycarbonyloxyethoxy)ethyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OCCOCCOC(=O)OCC=C JHQVCQDWGSXTFE-UHFFFAOYSA-N 0.000 description 3
- ATPPNMLQNZHDOG-UHFFFAOYSA-N 2-fluoro-2-phenylacetic acid Chemical compound OC(=O)C(F)C1=CC=CC=C1 ATPPNMLQNZHDOG-UHFFFAOYSA-N 0.000 description 3
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- PCGVEHCDYPVDET-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethylphosphonic acid Chemical compound COCCOCCP(O)(O)=O PCGVEHCDYPVDET-UHFFFAOYSA-N 0.000 description 2
- YHBWXWLDOKIVCJ-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]acetic acid Chemical compound COCCOCCOCC(O)=O YHBWXWLDOKIVCJ-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 125000003118 aryl group Polymers 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- OGDSVONAYZTTDA-UHFFFAOYSA-N tert-butylphosphonic acid Chemical compound CC(C)(C)P(O)(O)=O OGDSVONAYZTTDA-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- KEBBHXFLBGHGMA-UHFFFAOYSA-K aluminum;4-ethyl-3-oxohexanoate Chemical compound [Al+3].CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O KEBBHXFLBGHGMA-UHFFFAOYSA-K 0.000 description 1
- YNCDEEFMDXHURQ-UHFFFAOYSA-N aluminum;ethyl 3-oxobutanoate Chemical compound [Al].CCOC(=O)CC(C)=O YNCDEEFMDXHURQ-UHFFFAOYSA-N 0.000 description 1
- 230000000703 anti-shock Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 description 1
- BXLYLMZXSIDWCC-UHFFFAOYSA-N butan-2-yloxy(trihydroxy)silane Chemical compound CCC(C)O[Si](O)(O)O BXLYLMZXSIDWCC-UHFFFAOYSA-N 0.000 description 1
- BRXOKRLIIVYICJ-UHFFFAOYSA-N butoxy(trihydroxy)silane Chemical compound CCCCO[Si](O)(O)O BRXOKRLIIVYICJ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- MEXGMFLNFVSECQ-UHFFFAOYSA-N dimethoxy-methyl-[3-[2-(oxiran-2-ylmethoxy)ethoxy]propyl]silane Chemical compound CO[Si](C)(OC)CCCOCCOCC1CO1 MEXGMFLNFVSECQ-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- GCFHZZWXZLABBL-UHFFFAOYSA-N ethanol;hexane Chemical compound CCO.CCCCCC GCFHZZWXZLABBL-UHFFFAOYSA-N 0.000 description 1
- GYLXWHLPLTVIOP-UHFFFAOYSA-N ethenyl(2,2,2-trimethoxyethoxy)silane Chemical compound COC(OC)(OC)CO[SiH2]C=C GYLXWHLPLTVIOP-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002578 polythiourethane polymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 description 1
- XQVLEZMEMDWETM-UHFFFAOYSA-N trihydroxy-[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](O)(O)O XQVLEZMEMDWETM-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0047—Preparation of sols containing a metal oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Definitions
- the present invention relates to a process for the preparation of colloidal solutions of zirconia and to the incorporation of these colloidal solutions into different matrices such as anti-scratch and / or abrasion-resistant coatings for spectacle lenses or ophthalmic substrates, in particular particularly for spectacle lenses.
- colloids are also used in antireflection layers obtained by sol / gel as well as in anti-shock primers.
- colloids zirconia or zirconium oxide.
- Colloidal fillers such as colloidal silica or inorganic oxides, such as titanium, zirconium, tin or antimony oxide, having a high refractive index, are used in protective coatings for spectacle lenses. Their presence makes it possible to reinforce the hardness of the network constituted by the epoxysilane matrix and / or to increase the refractive index. In order to obtain the transparency of the coatings and to avoid light scattering, it is necessary to have colloids whose particles are of small size and which do not form aggregates.
- a first technical problem is to have a method for reproducibly obtaining small particle sizes, or nanoparticles, that is to say less than 50 nm, preferably less than 20 nm.
- a second technical problem to be solved is to prevent these particles from forming aggregates.
- Patent EP233343 describes the formation of soils consisting of such aggregates, which may be of interest as reinforcing fillers in polymers, but whose dimensions are not suitable for use in the ophthalmic field.
- Solutions of zirconia colloids must be stable over time. They must be compatible with many types of polymers such as ophthalmic lens substrates, sol / gel coatings, coatings photopolymerizable (meth) acrylates or thio (meth) acrylates, primers such as acrylic or polyurethane latices.
- polymers such as ophthalmic lens substrates, sol / gel coatings, coatings photopolymerizable (meth) acrylates or thio (meth) acrylates, primers such as acrylic or polyurethane latices.
- US patent application 2002/004544 describes the synthesis of an aqueous phase zirconia sol having an average particle size of less than 20 nm which comprises providing an aqueous solution comprising a zirconium polyether salt and hydrolyzing this salt under hydrothermal conditions at a temperature and pressure that allow crystallization.
- a cubic and / or tetragonal (predominantly) and monoclinic zirconia sol is obtained.
- the present invention provides an alternative solution to this technique, which has many advantages as will be apparent from the description below.
- a process for preparing a colloidal solution of non-agglomerated zirconia particles comprising the following steps: a) obtaining a suspension of zirconium hydroxide, preferably aqueous, b) adding to said suspension a mineral acid in a molar ratio [mineral acid] / [Zr] ⁇ 0.5, c) the hydrothermal treatment of said suspension, d) recovering the colloidal solution of zirconia particles.
- the suspension of zirconium hydroxide is obtained by basic treatment of an aqueous solution of zirconium oxychloride, preferably by adding an ammoniacal solution.
- the suspension of zirconium hydroxide is obtained by separating and purifying a zirconium hydroxide precipitate from said basic treatment, followed by redispersion in an aqueous medium of said precipitate.
- Said purification is preferably carried out by successive redispersion and filtration in deionized water.
- the pH of the suspension of zirconium hydroxide is preferably of the order of 7 in step a).
- An essential element of the invention consists in carrying out a hydrothermal treatment of the suspension of zirconium hydroxide at an acid content such that the molar ratio [mineral acid] / [Zr] is less than 0.5 and varies from 0 , 01 to less than 0.5, preferably 0.05 to 0.2. Indeed, if one proceeds to higher acid contents or in basic medium, one obtains either aggregates or poorly controlled particles.
- hydrochloric acid As useful mineral acids, mention may be made of hydrochloric acid, nitric acid, hydrochloric acid being preferred.
- the hydrothermal treatment is preferably carried out in an autoclave at a temperature of 150 to 200 ° C., and preferably of the order of 165 ° C., for a period of 3 hours to 3 days.
- the resulting soil comprises a mixture of tetragonal zirconia (majotary) and monoclinic.
- the solids content of the colloidal solution of zirconia preferably varies from 3 to 10%, preferably from 4 to 7% by weight.
- the method preferably comprises an additional step of grafting, on the surface of the zirconia particles of compounds carrying groups providing a steric and / or electrostatic repulsion between said zirconia particles.
- These compounds carrying groups providing a steric and / or electrostatic repulsion preferably comprise a carboxylic acid function or phosphonic or sulphonic acid ensuring their grafting.
- the process for preparing a zirconia sol comprises an additional step of incorporating a reactive solvent.
- a zirconia particle composition is thus obtained which is also the subject of the invention.
- the reactive solvent is introduced by redispersion of the zirconia particles, initially in aqueous medium, in the reactive solvent.
- a reactive solvent is defined as a monomer having a good affinity with the zirconia nanoparticles which allows their good dispersion, with, in addition, an acrylic or methacrylic function which allows incorporation into the thermosetting network by photopolymerization.
- the alcohol function is used to ensure redispersion.
- This reactive solvent is preferably hydroxyethyl methacrylate (HEMA).
- HEMA is a good solvent for the redispersion of zirconia: the alcohol function of the molecule ensures the good dispersion of the nanoparticles, whereas the methacrylate function makes it possible to incorporate the molecule in a thermosetting matrix.
- the zirconia particle composition comprises at least one additional monomer comprising at least two functions chosen from acrylate, methacrylate, thioacrylate and thiomethacrylate functional groups.
- the additional monomer is bisphenol-A 4-ethoxylated dimethacrylate or BMTES.
- poly (alkyl) acrylate substrates in particular those obtained by polymerization of alkyl methacrylates, in particular C 1 -C 4 alkyl methacrylates, such as methyl (meth) acrylate and ethyl (meth) acrylate, polyethoxylated aromatic (meth) acrylates such as polyethoxylated bisphenolate dimethacrylates, allyl derivatives such as allyl carbonates aliphatic or aromatic polyols, linear or branched, thio- (meth) acrylic, polythiourethane, polycarbonate (PC) and polyepisulfide substrates.
- alkyl methacrylates in particular C 1 -C 4 alkyl methacrylates, such as methyl (meth) acrylate and ethyl (meth) acrylate
- polyethoxylated aromatic (meth) acrylates such as polyethoxylated bisphenolate dimethacrylates
- allyl derivatives such as
- substrates obtained by polymerization of the allyl carbonates of polyols among which may be mentioned ethylene glycol bis allyl carbonate, diethylene glycol bis 2-methyl carbonate, diethylene glycol bis (allyl carbonate), ethylene glycol bis (2-chloro allyl carbonate), ethylene glycol bis (allyl carbonate), 1,3-propanediol bis (allyl carbonate), propylene glycol bis (2-ethyl allyl carbonate), 1,3-butylenediol bis (allyl) carbonate),
- 1,4-butenediol bis (2-bromo allyl carbonate), dipropylene glycol bis (allyl carbonate), trimethylene glycol bis (2-ethyl allyl carbonate), pentamethylene glycol bis (allyl carbonate), isopropylene bis phenol-A bis ( allyl carbonate).
- substrates obtained by polymerization of thio (meth) acrylic monomers such as those described in French patent application FR-A-2 734 827.
- the substrates can be obtained by polymerization. mixtures of the above monomers.
- the preferred substrates are the substrates obtained by photopolymerization.
- the content of zirconia particles in the substrates can vary in large proportions depending on the desired properties.
- the content of zirconia particles may vary from 0.1 to 50% by weight relative to the total weight polymer + particles, preferably from 10 to 40%.
- colloidal zirconia solutions can also be incorporated into soil / gel, anti-abrasion, or anti-glare coating compositions.
- the sol is prepared from at least one alkoxysilane such as an epoxysilane, preferably trifunctional, and / or a hydrolyzate thereof, obtained for example by hydrolysis with a solution of hydrochloric acid HCl.
- the duration of which is generally between 2 h and 24 h, preferably between 2 h and 6 h, catalysts are optionally added.
- a surfactant compound is also preferably added to promote the optical quality of the deposit.
- the preferred epoxyalkoxysilanes comprise an epoxy group and three alkoxy groups, the latter being directly bonded to the silicon atom.
- a preferred epoxyalkoxysilane may be an alkoxysilane bearing a ⁇ - (3,4-epoxycyclohexyl) group, such as ⁇ - (3,4-epoxycyclohexyl) ethylthmethoxysilane.
- Particularly preferred epoxyalkoxysilanes have formula (I):
- R 1 O 3 Si (CH 2 ) a (OCH 2 CH 2 ) b OCH 2 C- - -CH 2 (I) O in which: R 1 is an alkyl group of 1 to 6 carbon atoms, preferably a methyl or ethyl group,
- R 2 is a methyl group or a hydrogen atom, a is an integer from 1 to 6, b is 0, 1 or 2.
- epoxysilanes are ⁇ -glycidoxypropyltriethoxysilane or ⁇ -glycidoxypropyltrimethoxysilane.
- Preferentially ⁇ -glycidoxypropylthmethoxysilane is used.
- epoxydialkoxysilanes such as ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane and ⁇ -glycidoxyethoxypropylmethyldimethoxysilane can also be used.
- epoxydialkoxysilanes are preferably used at lower levels than the epoxytrialkoxysilanes mentioned above.
- R 3 and R 4 are chosen from substituted or unsubstituted alkyl, methacryloxyalkyl, alkenyl and aryl groups (examples of substituted alkyl groups are halogenated alkyls, in particular chlorinated or fluorinated alkyls);
- Z is an alkoxy, alkoxyalkoxy or acyloxy group;
- c and d represent 0, 1 or 2, respectively; and
- c + d represents 0, 1 or 2.
- This formula includes the following compounds: (1) tetraalkoxysilanes, such as methylsilicate, ethylsilicate, n-propylsilicate, isopropylsilicate, n-butylsilicate, sec-butylsilicate, and t-butylsilicate, and / or (2) thalkoxysilanes, trialkoxyalkoxylsilanes or thacyloxysilanes such as computethylthméthoxysilane, usethylthéthoxysilane, vinylthméthoxysilane, vinyltriethoxysilane, vinyltriméthoxyéthoxysilane, vinyltriacetoxysilane, phénylthméthoxysilane, phénylthéthoxysilane, ⁇ -chloropropyl-thméthoxysilane, ⁇ - thfluoropropylthméthoxysilane, togetherthacryloxyprop
- the silane hydrolyzate is prepared by adding water or a solution of hydrochloric acid or sulfuric acid to the silane (s). It is also possible to carry out the hydrolysis without adding solvents and simply by using the alcohol or carboxylic acid formed during the reaction between the water and the alkoxysilane (s). these solvents by other solvents, such as alcohols, ketones, alkyl chlorides, and aromatic solvents. Hydrolysis with an aqueous hydrochloric acid solution is preferred.
- the solution may also comprise other oxide particles than the zirconia particles.
- Such particles are silica particles, or particles of high refractive index such as particles of titanium oxide, antimony oxide, tin, tantalum, niobium.
- the colloidal solution of zirconia, in aqueous solution, or in organic solution, preferably in alcoholic solution, stabilized in ethanol, is then added to the sol / gel composition prepared above so as to obtain a desired mass loading ratio (preferably between 0.1% and 39% by weight relative to the mass of EST (theoretical dry extract).
- the sol / gel composition preferably comprises at least one hardening catalyst.
- curing catalysts examples include aluminum compounds, and in particular aluminum compounds chosen from: aluminum chelates, and compounds of formulas (III) or (IV) detailed below :
- R and R ' are straight or branched chain alkyl groups of 1 to 10 carbon atoms
- n is an integer of 1 to 3.
- an aluminum chelate is a compound formed by reacting an alcoholate or an aluminum acylate with nitrogen and sulfur-free sequestering agents containing oxygen as a coordination atom.
- the aluminum chelate is preferably chosen from the compounds of formula (V):
- X is a group OL in which L is an alkyl group of 1 to 10 carbon atoms
- Y is at least one ligand produced from a compound of formula (1) or (2):
- M 1 , M 2 , M 3 and M 4 are alkyl groups of 1 to 10 carbon atoms, and v is 0.1 or 2.
- Examples of compounds of formula (V) that may be mentioned are aluminum acetylacetonate, aluminum ethylacetoacetate bisacetylacetonate, aluminum bisethylacetoacetate acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate and diisopropoxide monohydrate. aluminum methylacetoacetate.
- aluminum acetylacetonate in a proportion of 0.1 to 5% by weight of the total weight of the composition, will preferably be used as a hardening catalyst for the composition.
- any conventional deposition process can be used to deposit the coating.
- dip coating a technique according to which the substrate to be coated is immersed in a bath of the composition, or the deposit by centrifugation.
- the sol is preferably deposited by "spin coating", that is to say by centrifugation, on substrates, for example an ORMA® substrate of Essilor, based on poly (diethylene glycol bisallyl carbonate).
- the deposition rate is between 100 rpm and 3000 rpm, preferably between 200 rpm and 2000 rpm.
- the varnishes are then cured, preferably by heat treatment in an oven for a period of 1 to 5 hours, typically 3 hours at a temperature between 80 ° C and 120 ° C.
- the films obtained typically have a thickness of 1 to 10 microns, preferably 2 to 5 microns.
- zirconia solutions obtained by the process of the invention can also be incorporated in a solution of adhesion or impact-resistant primer.
- Preferred primer compositions include thermoplastic polyurethane compositions, such as those described in Japanese Patents 63-141001 and 63-87223, poly (meth) acrylic primary compositions, such as those described in US Pat. US Pat. No. 5,015,523, the compositions based on thermosetting polyurethanes, such as those described in US Pat. And poly (meth) acrylic latex and polyurethane latex compositions, such as those disclosed in US 5,316,791, EP-0680492.
- Preferred primary compositions are polyurethane-based compositions and latex-based compositions, particularly polyurethane latices.
- the poly (meth) acrylic latices are copolymer latices consisting mainly of a (meth) acrylate, such as, for example, ethyl or butyl, methoxy or ethoxyethyl (meth) acrylate, with a generally minor proportion of at least one other comonomer, such as for example styrene.
- a (meth) acrylate such as, for example, ethyl or butyl, methoxy or ethoxyethyl (meth) acrylate
- at least one other comonomer such as for example styrene.
- Preferred poly (meth) acrylic latexes are acrylate-styrene copolymer latices.
- Such latexes of acrylate-styrene copolymers are commercially available from Zeneca Resins under the name Neocryl ®.
- Polyurethane latices are also known and commercially available.
- polyurethane latices containing polyester units By way of example, mention may be made of polyurethane latices containing polyester units. Such latexes are also marketed by Zeneca Resins under the name ® and NEOREZ by Baxenden Chemical Company under the name WITCOBOND ®.
- primer compositions may be deposited on the faces of the optical article by dipping or centrifugation and then dried at a temperature of at least 70 ° C. and up to 100 ° C., preferably of the order of 90 ° C, for a period of 2 minutes to 2 hours, generally of the order of 15 minutes, to form primer layers having thicknesses, after firing, of 0.2 to 2.5 ⁇ m, preferably 0, 5 to 1, 5 ⁇ m.
- the solids content of the colloid may preferably vary from 0.1 to 65%, preferably from 0.1 to 50%.
- Figures 1 to 3 zirconia particles in the colloidal solution according to the invention of the corresponding example 1 visualized by MET (transmission electron microscopy).
- Figures 4 zirconia particles in the colloidal solution of Example 2 (comparative) visualized by MET.
- the purified zirconium hydroxide cake is finally redispersed in a determined amount of water.
- the control of the acidity of the hydrothermal synthesis medium takes place at this stage of the preparation by addition of acid or base to the redispersion solution.
- the solution is carried out with vigorous stirring at first and then under sonification in a second step.
- the "milk" obtained is introduced into a teflon beaker.
- the assembly is then placed in an autoclave to proceed with the hydrothermal treatment. During this treatment the solution is stirred.
- an aqueous colloidal solution of zirconia is obtained. It is in the form of an opalescent solution with a slightly bluish tinge.
- the colloidal reference solution is carried out under the following experimental conditions:
- the stability of the soil obtained is improved by dialyzing it with a cellophane membrane for 7 days.
- Dry extract of the order of 6%. - The particles are represented at different magnifications
- Particle size around 10 nm ( Figures 1, 2); monocrystalline particles ( Figure 3).
- Example 2 (Comparative): The process of Example 1 is repeated, but using a molar ratio HCL / Zr of 1.
- the mixture is brought to 50 ° C for 1 h, after this treatment the treated zirconia precipitates.
- the precipitate is recovered by centrifugation. Part of the excess methacrylic acid is removed during this step. To completely rid the zirconia of unreacted acid the precipitate is suspended in hexane. After further centrifugation and removal of the supernatant the precipitate is easily redispersed in ethanol. In order to remove traces of hexane, the solvent (ethanol-hexane trace mixture) of the colloidal solution is then removed on a rotary evaporator. The solid obtained is definitively dispersed in a given quantity of ethanol or acetone to form a stable colloidal solution with a solids content greater than 30%. The zirconia thus modified is checked on an infrared spectrum (not shown) that the grafting has done well.
- the mixture is brought to 70 ° C for 1 h, after this treatment the treated zirconia precipitates.
- the precipitate is recovered by centrifugation. Part of the excess fluorophenylacetic acid is removed during this step.
- To completely rid the zirconia of the acid which did not react the precipitate is suspended in methanol and recovered by centrifugation. After 2 comparable washings the precipitate is finally redispersed in N-methyl-2-pyrrolidone (NMP) to form a stable colloidal solution with a solids content greater than 30%.
- NMP N-methyl-2-pyrrolidone
- the mixture is brought to 70 ° C. for 1 hour, after this treatment the treated zirconia is always perfectly dispersed. In order to get rid of the excess acid the colloidal solution is added dropwise in a large volume of acetone.
- the mixture is brought to 80 ° C. for 4 hours, after this treatment the treated zirconia precipitates.
- the precipitate is recovered by centrifugation. Some of the excess tert-butyl phosphonic acid is removed in this step. After washing with distilled water and centrifugation, the precipitate is dried under vacuum and redispersed in NMP.
- Examples of Zirconia Incorporation in Varnishes and Substrates Incorporation of non-functionalized zirconia nanoparticles could be carried out in thin layers and in photopolymerizable substrates.
- the incorporation process was carried out in two steps: 1. Redispersion of the nanoparticles, initially in the water Dl, in a solvent reactive by solvent exchange by evaporating the water on a rotary evaporator. 2. Polymerization, by UV or thermal radiation, by reacting the
- Photopolymerizable substrates could be made with good dispersion of zirconia nanoparticles at a rate of 20%.
- the zirconia sol used is the sol of Example 1.
- the zirconia nanoparticles initially in water, are redispersed in a reactive solvent by rotary evaporation (Rotavap):
- the vacuum is gradually established in the balloon and the vacuum is stabilized when a quiver appears on the surface of the liquid.
- Steps 1 and 2 are repeated until a pressure of 68 mbar is reached in the flask.
- Step 3 If water remains, continue with Step 3 until you have a maximum of 2% by weight of residual water. (The control of the purity is done by the mass control).
- the HEMA solution containing 35.8% of zirconia is stable, that is to say that it does not generate a precipitate.
- the 42.5% zirconia solution gives rise to the formation of a non-manipulable gel. However, this solution is stable.
- thermosetting network is obtained by the addition of a dysfunctional methacrylic reagent NS140 (bisphenol A 4 ethoxylated di (meth) acrylate) and BMTES make it possible to increase the refractive index of the reference matrix, and crosslink the system to improve its mechanical and chemical resistance.
- NS140 bisphenol A 4 ethoxylated di (meth) acrylate
- BMTES crosslink the system to improve its mechanical and chemical resistance
- 1.54), which makes it possible to consider limiting the index difference between the nanoparticles and the organic matrix.
- the mass percentage of photoinitiator, Irgacure 500 (CIBA) is 5% in the composition of the polymerized matrix (without HMP).
- HMP 4-hydroxy-4-methyl-2-pentanone / CAS: 123-42-2
- the solvent is totally evaporated at the polymerization of the varnish.
- the liquid index of the mixtures is measured using a thermostatic liquid refractometer (Reference: ATAGO 3T).
- the thickness and the index of the polymerized varnish is measured by reflection of the light on the substrate by an EOTECH device.
- the percentage of photoinitiator, CGI 819 is 0.1%.
- UV oven IST iron-doped lamp
- TEM Transmission electron microscopy
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Abstract
Description
Claims
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FR0754264 | 2007-04-04 | ||
PCT/FR2008/050606 WO2008139100A2 (fr) | 2007-04-04 | 2008-04-04 | Procede de preparation d'une solution colloïdale de zircone |
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FR2946973B1 (fr) | 2009-06-23 | 2011-08-12 | Univ Claude Bernard Lyon | Nouveau procede de preparation de nanoparticules a base de fluorure de terre rare |
KR101894056B1 (ko) | 2010-04-23 | 2018-10-04 | 픽셀리전트 테크놀로지스 엘엘씨 | 나노결정의 합성, 캐핑 및 분산 |
CN107416764A (zh) | 2010-10-27 | 2017-12-01 | 皮瑟莱根特科技有限责任公司 | 纳米晶体的合成、盖帽和分散 |
JP5922231B2 (ja) * | 2011-07-12 | 2016-05-24 | エシロール アンテルナシオナル (コンパニー ジェネラル ドプティック) | ジルコニアコロイドを生成するための方法 |
US9359689B2 (en) | 2011-10-26 | 2016-06-07 | Pixelligent Technologies, Llc | Synthesis, capping and dispersion of nanocrystals |
EP2610318A1 (fr) | 2011-12-30 | 2013-07-03 | Essilor International (Compagnie Générale D'Optique) | Composition de revêtement pour article optique comportant une suspension colloïdale de particules de zirconium |
CN105102376B (zh) * | 2012-12-26 | 2016-12-14 | 埃西勒国际通用光学公司 | 用于生产氧化锆胶体的方法 |
JP5758037B1 (ja) * | 2014-09-29 | 2015-08-05 | 第一稀元素化学工業株式会社 | 非晶質Zr−O系粒子を分散質とするゾル及びその製造方法 |
CN106277049B (zh) * | 2015-06-08 | 2017-08-15 | 北京化工大学 | 一种透明纳米氧化锆液相分散体及其制备方法与应用 |
CN105621480B (zh) * | 2016-01-25 | 2017-10-17 | 大连理工大学 | 一种采用低温煅烧锆溶胶制备二氧化锆纳米粉体的方法 |
FR3112770A1 (fr) | 2020-07-23 | 2022-01-28 | Mathym | Céramique d’oxyde métallique, ses précurseurs, sa préparation et son utilisation |
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JPH0712930B2 (ja) | 1985-12-10 | 1995-02-15 | 悦朗 加藤 | 単斜ジルコニア超微結晶の繊維束状配向凝集粒子および製造方法 |
JPH0729771B2 (ja) * | 1986-01-14 | 1995-04-05 | 悦朗 加藤 | 単斜ジルコニア超微結晶の高分散ゾルまたはゲルおよび製造方法 |
JPS6476919A (en) * | 1987-09-17 | 1989-03-23 | Toray Industries | Production of crystallized zirconia sol |
JP3284413B2 (ja) * | 1991-07-25 | 2002-05-20 | 東ソー株式会社 | 水和ジルコニアゾルおよびジルコニア粉末の製造方法 |
US5316791A (en) | 1993-01-21 | 1994-05-31 | Sdc Coatings Inc. | Process for improving impact resistance of coated plastic substrates |
JPH06321541A (ja) | 1993-05-18 | 1994-11-22 | Etsuro Kato | ジルコニア単分散球状超微粒子粉末の製造方法 |
US6376590B2 (en) * | 1999-10-28 | 2002-04-23 | 3M Innovative Properties Company | Zirconia sol, process of making and composite material |
US6656990B2 (en) | 2001-07-11 | 2003-12-02 | Corning Incorporated | Curable high refractive index compositions |
US7214726B2 (en) * | 2003-07-17 | 2007-05-08 | Kerr Corporation | Methods of using two-part self-adhering dental compositions |
US7074463B2 (en) | 2003-09-12 | 2006-07-11 | 3M Innovative Properties Company | Durable optical element |
JP4273942B2 (ja) * | 2003-11-28 | 2009-06-03 | Jsr株式会社 | ジルコニア粒子分散液、その製造方法及び光硬化性組成物 |
JP2005179111A (ja) * | 2003-12-18 | 2005-07-07 | Catalysts & Chem Ind Co Ltd | ジルコニアゾルの製造方法 |
JP4399592B2 (ja) * | 2004-03-10 | 2010-01-20 | 独立行政法人産業技術総合研究所 | 酸化ジルコニウム結晶粒子とその製造方法 |
US7241437B2 (en) * | 2004-12-30 | 2007-07-10 | 3M Innovative Properties Company | Zirconia particles |
WO2006099168A2 (fr) | 2005-03-11 | 2006-09-21 | 3M Innovative Properties Company | Compositions polymerisables renfermant des nanoparticules |
WO2006115043A1 (fr) * | 2005-04-18 | 2006-11-02 | Nissan Chemical Industries, Ltd. | Solution acide de zircone et son procede de fabrication |
JP4963820B2 (ja) * | 2005-09-02 | 2012-06-27 | 第一稀元素化学工業株式会社 | Zr−O系粒子を分散質とするゾルの製造方法 |
WO2007079144A1 (fr) * | 2005-12-29 | 2007-07-12 | 3M Innovative Properties Company | Compositions dentaires avec capteur d'eau |
JP2008201634A (ja) * | 2007-02-21 | 2008-09-04 | Fujifilm Corp | ジルコニア微粒子分散液、該分散剤から製造される有機無機複合材料および光学部品 |
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2008
- 2008-04-04 WO PCT/FR2008/050606 patent/WO2008139100A2/fr active Application Filing
- 2008-04-04 AT AT08788129T patent/ATE510800T1/de not_active IP Right Cessation
- 2008-04-04 EP EP08788129A patent/EP2142478B1/fr not_active Not-in-force
- 2008-04-04 US US12/594,560 patent/US8337788B2/en active Active
- 2008-04-04 JP JP2010501575A patent/JP2010523451A/ja active Pending
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Also Published As
Publication number | Publication date |
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WO2008139100A3 (fr) | 2009-01-08 |
EP2142478B1 (fr) | 2011-05-25 |
JP2010523451A (ja) | 2010-07-15 |
US20100144918A1 (en) | 2010-06-10 |
ATE510800T1 (de) | 2011-06-15 |
US8337788B2 (en) | 2012-12-25 |
WO2008139100A2 (fr) | 2008-11-20 |
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